Alkylation reaction using delaminated zeolite supports as catalysts

ABSTRACT

Provided is an improved alkylation process using a delaminated SSZ-70 catalyst. The process comprises contacting a hydrocarbon feedstock comprising olefins and isoparaffins with a catalyst comprising delaminated SSZ-70 under alkylating reaction conditions. The delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70. This prevents coke formation inside zeolite channels and improves catalyst stability.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional No. 62/074,974,filed Nov. 4, 2014, entitled “Alkylation Reaction Using DelaminatedZeolite Supports as Catalysts”, the contents of which are hereinincorporated by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to delaminated zeolites and their use ascatalysts in the hydroprocessing of hydrocarbons. More specifically, thepresent invention relates to the use of delaminated SSZ-70 as a catalystin the alkylation of hydrocarbons.

BACKGROUND

Zeolites are widely used as acidic catalysts for refining applicationsattributed to their unique and uniform pore structure with sizes in thesub-nanometer range. The pore sizes of zeolites dictate the reaction inrefining processes including hydroisomerization, hydrocracking, olefinalkylation and olefin oligomerization, and thus dictate reactionselectivity. However, hydroprocessing products often experience varyingdegrees of continuously (over)cracking when they diffuse out ofmicrometer-scale zeolitic channels. Thus elimination of these types ofside-reactions is significant for efficiency improvement. One of thesolutions for preventing overcracking is reduction of acidic strength.But this approach reduces the catalyst activity at the same time.

A. Corma et al. in “Delaminated zeolite precursors as selective acidiccatalysts”, Nature, vol. 396, November 1998, pp 353-356, discussesdelaminating MCM-22(P), the precursor of both MCM-22 and ERB-1 zeolites.The delaminated zeolite is designated ITQ-2, and was shown to havecatalytic potential.

Molecular sieve SSZ-70 is known and is discussed in “PhysiochemicalProperties and Catalytic Behavior of the Molecular Sieve SSZ-70”, Archeret al. Chemistry of Materials, 2010, vol. 22, pp 2563-2572. A method forthe synthesis of the SSZ-70 is discussed. Pure silica, borosilicate andaluminosilicate SSZ-70 materials were prepared and characterized. Thecatalytic activity of Al-SSZ-70 materials were tested using the CI(Constraint Index) test. U.S. Pat. Nos. 7,108,843 and 7,550,073 alsodiscuss the synthesis of the molecular sieve SSZ-70, and its use inhydrocarbon conversion processes such as hydrocracking The disclosure ofboth U.S. Pat. Nos. 7,108,843 and 7,550,073 are expressly incorporatedherein by reference in their entirety.

Providing a process for olefin alkylation to achieve a high qualityalkylate would be quite useful for gasoline blending, as long as thecatalyst exhibits good selectivity and stability.

SUMMARY

Provided is a process of alkylating hydrocarbons in the presence of acatalyst comprising delaminated SSZ-70. The delaminated SSZ-70 has beenfound to provide unexpected improvements in the catalysis ofhydroprocessing hydrocarbons. It has been found that delaminated SSZ-70offers a zeolite layer with a single unit cell of thickness in onedimension, allowing an elimination of mass transfer in comparison withregular SSZ-70 (non-delaminated). This prevents coke formation insidezeolitic channels and improves catalyst stability. The delaminatedSSZ-70 zeolite also exhibits features of maintaining zeolite strengthand spatial constraint of internal zeolitic framework. This providesopportunities to control novel chemistry by tailoring location of acidicsites for chemical reactions.

Among other factors, an improved alkylation process has been discoveredwhich comprises contacting a hydrocarbon feedstock comprising olefinsand isoparaffins with a catalyst comprising delaminated SSZ-70 underalkylating reaction condition. Superior selectivity and catalyststability is achieved for the reaction of olefins and isoparaffins. Theresulting product is a high quality alkylate useful for gasoline orgasoline blending.

BRIEF DESCRIPTION OF THE DRAWING

The Figure depicts acid sites on delaminated SSZ-70. It shows thepossibility of preparing SSZ-70-based catalysts with a varying locationof acidic sites, for example, (i) zeolitic acidic sites on both externaland internal surface, (ii) zeolitic acidic sites on internal surfaceonly, (iii) zeolitic acidic sites on external surface only.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to an improved alkylation process whichallows one to achieve superior selectivity and catalyst stability. Theprocess comprises contacting a hydrocarbon feed comprised ofisoparaffins and olefins under alkylation conditions with a catalystcomprising delaminated SSZ-70. It has been found that delaminated SSZ-70offers a zeolite layer with a single unit cell of thickness in onedimension, allowing an elimination of mass transfer in comparison withregular SSZ-70. The result is superior selectivity.

The delaminated SSZ-70 also exhibits features of maintaining zeoliticacidic strength and spatial constraint of the internal zeoliteframework. This provides one with the opportunity of controlling novelchemistry by tailoring the location of acidic sites. Turning to theFigure, three scenarios are schematically provided of controlledlocation of acidic sites that can be prepared with starting materials ofdelaminated SSZ-70 in either the Al- or B-form.

The molecular sieve SSZ-70 is known, as is synthesis thereof. U.S. Pat.No. 7,108,843, issued Sep. 19, 2006, for example describes the molecularsieve SSZ-70 and a synthesis for preparing the molecular sieve. TheSSZ-70 is characterized in U.S. Pat. No. 7,108,843 by its X-raydiffraction pattern before calcination and by its X-ray diffractionpattern after calcination. The disclosure of U.S. Pat. No. 7,108,843 ishereby expressly incorporated by reference herein in its entirety.

The delaminated SSZ-70 can be obtained by delaminating the SSZ-70molecular sieve using conventional techniques of delamination. In oneembodiment, the techniques described in U.S. 2012/0148487, publishedJun. 14, 2012, would be quite effective, which publication is expresslyincorporated herein by reference in their entirety.

In general, an aqueous mixture of chloride and fluoride anions, e.g.,alkylammoniumhalides and the SSZ-70 is prepared. The aqueous mixture ismaintained at a pH less than 12, e.g., about 9, and maintained at atemperature in the range of 5-150° C. for a length of time sufficient toeffect the desired delamination. The oxide product is then recovered,e.g., by acidification to a pH of about 2 followed by centrifugation.

In one embodiment, a non-aqueous mixture of chloride and fluorideanions, i.e., a mixture comprising an organic solvent, is maintained ata temperature in the range of from 5-150° C. to effect desireddelamination. The organic solvent can be any suitable organic solventwhich swells the starting material such as dimethyl formamide (DMF). Thedelaminated product can then be recovered from the mixture. Generally,acidification is used to recover the product. Sonication prior torecovery need not be employed, but sonification can be employed in theprocess if desired.

The chloride and fluoride anions can be obtained from any source of theanions. Any compound which will provide the anions in aqueous solutioncan be used. The cation is generally not important. Providing thefluoride and chloride anions is important. Bromide anions can also bepresent, but both fluoride and chloride anions must be present. Thecations can be any cation, with the use of alkylammonium cations beingsuitable in one embodiment. The alkyl group of such a cation can be anylength, and in one embodiment ranges from 1-20 carbons.Tetrabutylammonium cations in particular have been found useful. Themolar ratio of chloride to fluoride anions can be 100 or less, generallyfrom 100:1 to 1:100. In one embodiment, the ratio can range from 50:1 to1:50. It is the combination of the fluoride and chloride anions whichhas been discovered to be important.

The pH used in the synthesis when an aqueous mixture is used is lowerthan that generally used in delamination synthesis. The pH is generally12 or less, but can be any pH which does not transform the silica in thezeolite to create an amorphous silica phase. A pH of 12 or lessgenerally accomplishes this task and thereby allows one to obtain adelaminated layered zeolite precursor material substantially without anamorphous phase. In another embodiment, the pH is 11 or less, and even10 or less, with a pH of about 9 or less also being quite advantageous.A pH of approximately 9 is typically used in fluoride-mediated synthesisof zeolites.

The temperature used in the process for either the aqueous ornon-aqueous mixture can range widely. In general a temperature for theaqueous solution of from 5-150° C. is suitable. In another embodiment,the temperature can range from 50-100° C.

The length of time the zeolite is allowed to swell, and delaminate, inthe aqueous solution can vary greatly. Generally, the time can vary from30 minutes to one month. In one embodiment, the time ranges from 2 hoursto 50 hours. In another embodiment, the time can range from 5 to 20hours prior to collection of the product.

The delaminated oxide product is collected using conventional techniquessuch as centrifugation. An acid treatment step can be employed prior tocentrifugation, and may be conveniently conducted by contacting theswollen or partially delaminated layered zeolite precursor material witha strong acid, e.g., a mineral acid such as hydrochloric acid or nitricacid, at low pH, e.g., pH 2. Collection of the resulting oxide materialproduct can be performed by centrifugation.

The delaminated SSZ-70 is useful in a process for the alkylation ofolefins with isoparaffins for making alkylate. The process comprisescontacting C₂ to C₁₆ olefins and C₄-C₁₀ isoparaffins under olefinalkylation conditions in the presence of a catalyst comprising thedelaminated SSZ-70. The catalyst can comprise pure delaminated SSZ-70 orin mixture with any suitable conventional catalyst, and can be presentin the catalyst in amounts as small as 2 parts by weight. Generally, thecatalyst will comprise at least 2 parts by weight of the delaminatedSSZ-70.

The delaminated SSZ-70 can also be used for removing benzene fromgasoline by alkylating the benzene with olefins.

For high catalytic activity, the delaminated SSZ-70 zeolite can be inany form, but is preferred predominantly in its hydrogen ion form. It ispreferred that, after calcination, at least 80% of the cation sites areoccupied by hydrogen ions and/or rare earth ions.

Examples of suitable alkylation feedstocks which may be alkylated by thepresent process of the invention include various streams in a petroleumrefinery, a gas-to-liquid conversion plant, a coal-to-liquid conversionplant, or in naphtha crackers, middle distillate cracker or waxcrackers, FCC off-gas, FCC light naphtha, coker off-gas, coker naphtha,hydrocracker naphtha, and the like. Such streams generally containisoparaffin(s) and/or olefin(s). Such streams can be fed to the reactorof a hydrocarbon conversion system of the present invention via one ormore feed dryer units.

Examples of separate olefin containing streams include FCC off-gas,coker gas, olefin metathesis unit off-gas, polyolefin gasoline unitoff-gas, methanol to olefin unit off-gas, FCC light naphtha, coker lightnaphtha, Fischer-Tropsch unit condensate, and cracked naphtha. Someolefin containing streams may contain two or more olefins selected fromethylene, propylene, butylenes, pentenes, and up to C₁₆ olefins.

The olefin containing stream can be a fairly pure olefinic hydrocarboncut or can be a mixture of hydrocarbons having different chain lengthsthus a wide boiling range. The olefinic hydrocarbon can be terminalolefin (an alpha olefin) or can be an internal olefin (having aninternal double bond). The olefinic hydrocarbon chain can be eitherstraight chain or branched or a mixture of both. In one embodiment ofthe present invention, the olefinic feed may comprise a mixture ofmostly linear olefins from C₂ to about C₁₆. The olefins may be mostly,but not entirely, alpha olefins. In another embodiment of the presentinvention, the olefinic feed can comprise 50% of a single alpha olefinspecies. In another embodiment of the present invention, the olefinicfeed can comprise at least 20% of alpha olefin species.

In one embodiment, olefins in the feed may also undergo oligomerizationwhen contacted with delaminated SSZ-70 catalyst in the hydrocarbonconversion zone. Delaminated SSZ-70 catalyzed olefin oligomerization maytake place under the same or similar conditions as theolefin-isoparaffin alkylation process. As a result, in an embodiment ofthe present invention, both olefin oligomerization andolefin-isoparaffin alkylation may take place in a single reaction zoneof the hydrocarbon conversion process. In one embodiment of the presentinvention, an oligomeric olefin produced may be subsequently alkylatedby an isoparaffin to provide a distillate, and/or lubricant component orbase oil product.

Examples of isoparaffin containing streams include, but are not limitedto, FCC naphtha, hydrocracker naphtha, coker naphtha, Fisher-Tropschunit condensate, and cracked naphtha. Such streams can comprise amixture of two or more isoparaffins. In a one embodiment, the feed for adelaminated SSZ-70 catalyzed process can comprise isobutane, which maybe obtained, for example, from a hydrocracking unit, or may bepurchased.

Suitable olefins for the alkylation of an aromatic hydrocarbon are thosecontaining 2 to 16, preferably 2 to 4, carbon atoms, such as ethylene,propylene, butene-1, trans-butene-2 and cis-butene-2, or mixturesthereof. There may be instances where pentenes are desirable. Thepreferred olefins are butenes. Longer chain alpha olefins may be used aswell.

When alkylation of isoparaffins and olefins is the process conducted,reaction conditions can be as follows. It is preferred that the molarratio of isoparaffins to olefins be greater than four-to-one to preventrapid catalyst fouling. The reaction temperature may range from 100° F.to 600° F., preferably 250° F. to 450° F. The reaction pressure shouldbe sufficient to maintain at least a partial liquid phase in order toretard catalyst fouling. This is typically 50 psig to 1000 psigdepending on the feedstock and reaction temperature. Contact time mayrange from 10 seconds to 10 hours, but is usually from 5 minutes to anhour. The weight hourly space velocity (WHSV), in terms of grams(pounds) of isoparaffins and olefins per gram (pound) of catalyst perhour, is generally within the range of about 0.5 to 50.

In one embodiment, the delaminated SSZ-70 catalyst comprises a noblemetal selected from the group consisting of nickel (Ni), palladium (Pd),platinum (Pt), ruthenium (Ru), rhodium (Rh), iron (Fe), gold (Au),silver (Ag) and mixtures thereof. In another embodiment, the delaminatedSSZ-70 catalyst contains at least one metal selected from Groups 6through 8 of the Periodic Table.

The deactivated catalyst can be regenerated by hydrogenation orhydrocracking of coke or heavy hydrocarbons deposited on its surfaceunder hydrogenation and hydrocracking reaction conditions.

The following examples are provided to further illustrate the presentinvention, and are not meant to be limiting.

EXAMPLE Preparation of Al-SSZ-70

7.67 g aluminum hydroxide (Reheis F-2000) was added to 395.55 g NaOH(1M) in a 1 gallon liner. 240 g Cabosil fumed silica was slowly addedwhile stirring. At the same time, 1707.47 g 1,3-diisobutylimidazoliumhydroxide (9 wt %, SDAOH-1) and 149.27 g deionized water was added tothe liner. The final molar composition was 1SiO₂:0.01Al₂O₃:0.2SDAOH-1:0.1NaOH:30H₂O. The liner was placed into a 1 gallon, overheadstirred autoclave. The temperature was increased to 160° C. with a ramptime of 8 h and a stir rate of 150 rpm. The reaction mixture wassynthesized for 120 h. The final solids were filtered and washed withdeionized water to a conductivity of <50 μS/cm.

Preparation of B-SSZ-70

2.91 g H₃BO₃ was added to 84.20 g NaOH (1M) in a 1 L Teflon liner. 50.52g of Cabosil fumed silica was slowly added while stirring. At the sametime, 413.6 g 1,3-Bis(cyclohexyl)imidazolium hydroxide (0.40 M, SDAOH-2)was added to the liner. The final molar composition was1SiO₂:0.03B₂O₃:0.2SDAOH-2:0.1NaOH:30H₂O. The liner was placed into a 1L, overhead stirred, Parr autoclave. The temperature was increased to160° C. with a ramp time of 8 h and a stir rate of 70 rpm. The reactionmixture was synthesized for 116 h. The final solids were filtered andwashed with deionized water to a conductivity of 26 μS/cm.

Preparation of Delaminated B-SSZ-70

5 g of as-made B-SSZ-70 was added to a 500 mL, 1-neck, round-bottomflask. 200 mL N,N-dimethylformamide, 5.5 g cetyltrimethylammoniumbromide, 8.5 g tetrabutylammonium fluoride trihydrate, and 8.5 gtetrabutylammonium chloride were added to the flask. The contents of theflask were stirred in a 95° C. oil bath for 48 h. The contents of theflask were then poured into a 500 mL wide-mouth bottle and sonicated inan ice bath for 2 h using a sonicator made by Sonics and Materials Inc.(Vibracell VC 750, 35% power) operating under pulse mode (4 s on and 1 soff). The delaminated solution was divided into four equal parts andpoured into four 250 mL centrifuge bottles. 200 mL tetrahydrofuran wasadded to each centrifuge bottle, and the bottles were centrifuged at8500 rpm (11000 g) for 10 min. The solution was decanted, 250 mL freshTHF was added to each bottle, and the solids were redispersed into thesolution. The bottles were centrifuged and decanted. 250 mL diethylether was added to each bottle and the solids were redispersed into thesolution. The bottles were centrifuged, decanted, and the solids weredried at 80° C. The sample was calcined at 550° C. for six hours at aramp rate of 1° C./min in flowing air.

Preparation of Al-Exchanged Delaminated Al-SSZ-70

3 g of delaminated B-SSZ-70 was added to a 250 mL, 1-neck, round-bottomflask. 75 g deionized water and 11.25 g aluminum nitrate nonahydratewere added to the flask. The contents of the flask were stirred in a 95°C. oil bath for 96 h. The mixture was filtered and washed with 300 mLHCl (pH=2). The mixture was filtered and washed with another 300 mL HCl.The mixture was filtered and washed with deionized water to a pH of 7.The solids were dried at 80° C.

Preparation of a Catalyst Base Containing 10% Al-SSZ-70 (CatalystBase-A, Base Case)

A comparative catalyst was prepared per the following procedure: 90parts by weight pseudo boehmite alumina powder (obtained from Sasol),and 10 parts by weight of Al-SSZ-70 zeolite were mixed well. The SSZ-70zeolite employed had the following properties: a SiO₂/Al₂O₃ mole ratioof about 80. A diluted HNO₃ acid aqueous solution (1 wt. %) was added tothe mix powder to form an extrudable paste. The paste was extruded in1/16 inch asymmetric quadrilobe shape, and dried at 250° F. (121° C.)overnight. The dried extrudates were calcined at 850° F. (454° C.) for 1hour with purging excess dry air and cooled down to room temperature.

Preparation of 0.5wt % Pt Catalyst Containing 10% Al-SSZ-70 (Catalyst-A,Base Case)

Impregnation of Pt metal was done using an aqueous solution containing3.3% Pt salt in concentrations equal to the target metal loadings of 0.5wt. % Pt based on the bulk dry weight of the finished catalyst. Thetotal volume of the solution matched the 103% water pore volume of theabove calcined base extrudate sample (incipient wetness method). Themetal solution was added to the base extrudates of base-A (base case)gradually while tumbling the extrudates. When the solution addition wascompleted, the soaked extrudates were aged for 2 hours. Then theextrudates were dried at 250° F. (121° C.) overnight. The driedextrudates were calcined at 662° F. (350° C.) for 1 hour with purgingexcess dry air, and cooled down to room temperature. The performance ofthis catalyst was evaluated with nC16 pure compound.

Preparation of a New Catalyst Base Containing 10% Delaminated Al-SSZ-70(Catalyst Base-B)

A new isomerization-improved catalyst base was prepared per thefollowing procedure: 90 parts by weight pseudo boehmite alumina powder(obtained from Sasol), and 10 parts by weight of delaminated Al-SSZ-70zeolite were mixed well. A diluted HNO₃ acid aqueous solution (1 wt. %)was added to the mix powder to form an extrudable paste. The paste wasextruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250° F.(121° C.) overnight. The dried extrudates were calcined at 850° F. (454°C.) for 1 hour with purging excess dry air and cooled down to roomtemperature.

Preparation of 0.5 wt % Pt Catalyst Containing 10% Delaminated Al-SSZ-70(Catalyst-B)

Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5wt. % Pt based on the bulk dry weight of the finished catalyst. Thetotal volume of the solution matched the 103% water pore volume of theabove calcined base extrudate sample (incipient wetness method). Themetal solution was added to the base extrudates of base-B graduallywhile tumbling the extrudates. When the solution addition was completed,the soaked extrudates were aged for 2 hours. Then the extrudates weredried at 250° F. (121° C.) overnight. The dried extrudates were calcinedat 662° F. (350° C.) for 1 hour with purging excess dry air, and cooleddown to room temperature. The performance of this catalyst was evaluatedwith nC₁₆ pure compound.

Preparation of a Catalyst New Base Containing 2% Delaminated Al-SSZ-70(Catalyst Base-C)

A new isomerization-improved catalyst base was prepared per thefollowing procedure: 25 parts by weight pseudo boehmite alumina powder(obtained from Sasol), 73 parts by weight of silica-alumina powder(obtained from Sasol), and 2 parts by weight of delaminated Al-SSZ-70zeolite were mixed well. A diluted HNO₃ acid aqueous solution (1 wt. %)was added to the mix powder to form an extrudable paste. The paste wasextruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250° F.(121° C.) overnight. The dried extrudates were calcined at 850° F. (454°C.) for 1 hour with purging excess dry air and cooled down to roomtemperature.

Preparation of 0.5 wt % Pt Catalyst Containing 2% Delaminated Al-SSZ-70(Catalyst-C)

Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5wt. % Pt based on the bulk dry weight of the finished catalyst. Thetotal volume of the solution matched the 103% water pore volume of theabove calcined base extrudate sample (incipient wetness method). Themetal solution was added to the base extrudates of base-C graduallywhile tumbling the extrudates. When the solution addition was completed,the soaked extrudates were aged for 2 hours. Then the extrudates weredried at 250° F. (121° C.) overnight. The dried extrudates were calcinedat 662° F. (350° C.) for 1 hour with purging excess dry air, and cooleddown to room temperature. The performance of this catalyst was evaluatedwith nC16 pure compound.

Preparation of a New Catalyst Base Containing 3% Delaminated B-SSZ-70(Catalyst Base-D)

A new isomerization-improved catalyst base was prepared per thefollowing procedure: 25 parts by weight pseudo boehmite alumina powder(obtained from Sasol), 72 parts by weight of silica-alumina powder(obtained from Sasol), and 3 parts by weight of delaminated B-SSZ-70zeolite were mixed well. A diluted HNO₃ acid aqueous solution (1 wt. %)was added to the mix powder to form an extrudable paste. The paste wasextruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250° F.(121° C.) overnight. The dried extrudates were calcined at 850° F. (454°C.) for 1 hour with purging excess dry air and cooled down to roomtemperature.

Preparation of 0.5 wt % Pt Catalyst Containing 3% Delaminated B-SSZ-70(Catalyst-D)

Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5wt. % Pt based on the bulk dry weight of the finished catalyst. Thetotal volume of the solution matched the 103% water pore volume of theabove calcined base extrudate of base-D (incipient wetness method). Themetal solution was added to the base extrudates gradually while tumblingthe extrudates. When the solution addition was completed, the soakedextrudates were aged for 2 hours. Then the extrudates were dried at 250°F. (121° C.) overnight. The dried extrudates were calcined at 662° F.(350° C.) for 1 hour with purging excess dry air, and cooled down toroom temperature. All the catalysts and their supports werecharacterized as follows:

Brönsted acidity: determined by isopropylamine-temperature-programmeddesorption (IPam TPD) adapted from the published descriptions by T. J.Gricus Kofke, R. K. Gorte, W. E. Farneth, J. Catal. 114, 34-45, 1988; T.J. Gricus Kifke, R. J. Gorte, G. T. Kokotailo, J. Catal. 115, 265-272,1989; J. G. Tittensor, R. J. Gorte and D. M. Chapman, J. Catal. 138,714-720, 1992. Samples are pre-treated at 400-500° C. for 1 hour inflowing dry H₂. The dehydrated samples are then cooled down to 120° C.in flowing dry He and held at 120° C. for 30 minutes in a flowing Hesaturated with isopropylamine for adsorption. Theisopropylamine-saturated samples are then heated up to 500° C. at a rateof 10° C./min in flowing dry He. The Brönsted acidity is calculatedbased on the weight loss vs. temperature by TGA and effluent NH₃ andpropene by Mass Spectrometer.

Surface area: determined by N₂ adsorption at its boiling temperature.BET surface area is calculated by the 5-point method at P/P₀=0.050,0.088, 0.125, 0.163, and 0.200. Samples are first pre-treated at 400° C.for 6 hours in the presence of flowing, dry N₂ so as to eliminate anyadsorbed volatiles like water or organics.

TABLE 1 Properties of calcined catalyst bases containing Al-SSZ-70 anddelaminated Al-SSZ-70 Ext. Brönsted Micropore SA, acidity, Catalyst baseZeolite volume, cc/g m2/g μmol/g Base-A Original SSZ-70 (w/o 0.0214 207161 (base case) delaminated) Base-B Delaminated SSZ-70 0.0068 277 131

The high external surface area of the support of the new catalyst base-Bin comparison with the base case catalyst support of catalyst base-A iscontributed to the high external surface area of delaminated Al-SSZ-70.In contrast to the base case catalyst base-A, the delaminatedSSZ-70-containing catalyst base-B showed a lower micropore volume.Delaminated SSZ-70 showed less Brönsted acidic density than its originalprecursor.

TABLE 2 Properties of calcined catalyst bases containing delaminatedAl-SSZ-70 and delaminated B-SSZ-70 Surface Pore Mesopore Brönsted Area,volume, size, acidity, Catalyst base Zeolite m2/g cm3/g nm μmol/g Base-C2% 421 0.81 11.3 142 Delaminated Al-SSZ-70 Base-D 3% 420 0.80 11.2 158Delaminated B-SSZ-70

The high Brönsted acidity of the catalyst base-D suggests Al exchangedto the B site of zeolite framework during the extrusion process. Thus,it is concluded that the Al exchange process can be eliminated in thepreparation of hydroprocessing catalysts using delaminated B-SSZ-70zeolite.

It is expected that if the delaminated SSZ-70, whether in thedelaminated Al-SSZ-70 or B-SSZ-70 form, was used in an alkylationreaction between isoparaffins and olefins, exceptional stability andselectivity would be observed.

The above specification, examples and data provide a completedescription of the manufacture and use of the composition of theinvention. Since many embodiments of the invention can be made withoutdeparting from the spirit and scope of the invention, the inventionresides in the claims hereinafter appended.

What is claimed is:
 1. A hydrocarbon conversion process comprisingcontacting a hydrocarbon feedstock with a catalyst comprisingdelaminated SSZ-70 under alkylating reaction conditions.
 2. The processof claim 1, wherein the hydrocarbon feedstock comprises olefins andisoparaffins.
 3. The process of claim 1, wherein olefins are alkylatedby isoparaffins.
 4. The process of claim 3, wherein olefins areoligomerized, and then the oligomerized olefins are alkylated byisoparaffins.
 5. The process of claim 3, wherein the alkylating reactionproduces high quality alkylate for gasoline or gasoline blending.
 6. Theprocess of claim 2, wherein the delaminated SSZ-70 is predominantly inthe hydrogen form.
 7. The process of claim 2, wherein the catalystfurther comprises at least one noble metal.
 8. The process of claim 2,wherein the delaminated SSZ-70 is a delaminated Al-SSZ-70 material. 9.The process of claim 2, wherein the delaminated SSZ-70 is a delaminatedB-SSZ-70 material.
 10. The process of claim 2, wherein the delaminatedSSZ-70 can be regenerated under hydrogenation or hydrocracking reactionconditions.
 11. The process of claim 2, wherein the olefins comprise C₂to C₁₆ olefins.
 12. The process of claim 11, wherein the olefinscomprise greater than 50% linear olefins.
 13. The process of claim 2,wherein the isoparaffins comprise C₄ to C₁₀ isoparaffins.
 14. Theprocess of claim 2, wherein the molar ratio of isoparaffins to olefinsis greater than four.